Aerosol and Air Quality Research, 15: 1737–1747, 2015

Copyright © Taiwan Association for Aerosol Research

ISSN: 1680-8584 print / 2071-1409 online
doi: 10.4209/aaqr.2014.12.0333

Pollution Properties of Water-Soluble Secondary Inorganic Ions in Atmospheric

PM2.5 in the Pearl River Delta Region

Dingli Yue1, Liuju Zhong1*, Tao Zhang1, Jin Shen1, Yan Zhou1, Limin Zeng2, Huabin Dong3,
Siqi Ye1
1
Guangdong Environmental Monitoring Center, State Environmental Protection Key Laboratory of Regional Air Quality
Monitoring, Guangzhou 510308, China
2
Peking University, State Key Joint Laboratory of Environmental Simulation and Pollution Control, Beijing 100871,
China
3
Institute of Atmospheric Physics, Chinese Academy of Sciences, Beijing 100029, China

ABSTRACT

Based on the online observation of PM2.5 mass concentration, its water-soluble inorganic ions, and their gaseous
precursors during August of 2013 to March of 2014 at the atmospheric supersite in the Pearl River Delta (PRD) region, the
inter-action of the secondary compositions and their precursors was discussed, and the pollution properties of the
secondary inorganic ions were revealed. During the whole measurement period, the average concentrations of SO42–, NO3–
and NH4+ were 16.6 µg m–3, 9.0 µg m–3 and 10.2 µg m–3, respectively, with total contribution to PM2.5 of 55.8%, indicating
the significant role of secondary transformation in PM2.5 pollution. The seasonal average total contributions of SO42–, NO3–
and NH4+ to PM2.5 varied from 46.0% to 64.3%, lowest in summer and highest in winter. The contributions of SO42– and
NH4+ to PM2.5 were relatively stable; while those of NO3– in different seasons were distinct, even dominating PM2.5 in
some pollution cases in winter. NH3 was abundant with an annual average concentration of 15.2 µg m–3, facilitating the
neutralization of H2SO4 and HNO3 with the average [NH4+]/(2[SO42–] + [NO3–]) equivalent charge ratio of 1.1. The
maximum daily peak concentration of HNO3 was as high as 18.6 µg m–3, providing an evidence for the strong oxidizing
property of the atmosphere in the PRD region. The theoretical equilibrium constant (Ke) of NH4NO3 is always lower than
the observed concentration product (Km = [NH3] × [HNO3]) in spring and winter with higher HNO3 concentrations; while
in over 60% of the time during summer and autumn, mainly during daytime, Ke was higher. In general, the strong
oxidizing property and NH3 played important roles in the fine particle pollution in the PRD region.

Keywords: PM2.5; Water-soluble inorganic ions; Secondary transformation; Gas-particle conversion.

INTRODUCTION PM2.5 vary with seasons, presenting generally high values in

Atmospheric aerosols influence our life in many aspects.
They impose obvious effects on the global climate change
and human health (Dockery et al., 1994; Nel, 2005), and
visibility degradation (Sokolik and Toon, 1996; Jung and
Kim, 2006). Consequently, more and more attention has
been paid to them in recent years. It is well known that
aerosols with different compositions and from diverse sources
have distinct effects. In order to understand their effects and
provide scientifically sound evidence for effective control
policies making, accurate knowledge on physical and
chemical properties of aerosol is urgently required. Previous
studies showed that concentrations and compositions of
*
Corresponding author.
E-mail address: zhongliuju@139.com
winter and low ones in summer in general; and carbonaceous
matter and water-soluble ions such as sulfate (SO42–),
nitrate (NO3–) and ammonium (NH4+) are usually the main
contributors. HNO3 and H2SO4 can be transformed into
aerosol by neutralization reactions (Seinfeld and Pandis,
1998). Semi-volatile NH4NO3 is formed via reversible phase
equilibrium with NH3 and HNO3 (Pio and Harrison, 1987).
Such equilibrium between gas- and particle-phase is strongly
influenced by ambient temperature (T) and relative humidity
(RH) (Mozurkewich, 1993).
The Pearl River Delta (PRD) region is one of the biggest
city clusters with extremely invigorating economy and dense
population in the world. Rapid urbanization and economic
development have been accompanied by the serious
deterioration of regional air quality as well as significant
changes of air pollution properties: emissions of primary
pollutants such as SO2 and inhalable particulate matter
(PM10) have been greatly reduced by certain abatement
1738 Yue et al., Aerosol and Air Quality Research, 15: 1737–1747, 2015
measures, while formations of secondary products such as
ozone and fine particles in high concentrations have become
the main issues, especially after the National Ambient Air
Quality Standards (GB 3095-2012) was promulgated. The
chemical compositions of PM2.5 and PM10 in the PRD
region have been reported before (e.g., Cao et al., 2004;
Hagler et al., 2006; Liu et al., 2008; Yue et al., 2010a;
Huang et al., 2014). The gaseous precursors are crucial to
investigate their formation mechanisms and behaviors in the
atmosphere. However, simultaneous on-line measurements of
water-soluble ions of PM2.5 and related precursor gases
(HNO3, SO2 and NH3) are still very rare (Hu et al., 2008),
and seasonal variations of them has not been reported in
this region. In this study secondary water-soluble inorganic
ions, including SO42–, NO3– and NH4+ in PM2.5, and the
related gaseous pollutants including HNO3, NH3, SO2 and
NO2 were measured simultaneously at a regional atmospheric
supersite in the PRD region of Guangdong Province (Zhong
et al., 2013) during four different seasons. The goal of this
study was to understand the inter-action of the secondary
water-soluble ions and their gaseous precursors and thus to
reveal the pollution properties of the secondary inorganic
ions in the PRD region, providing scientific support for
designing effective fine particle pollution control strategies.
METHODOLOGY
Observation Site and Periods
The measurements were conducted at the Guangdong
Atmospheric Supersite located in Taoyuan Town, Heshan
county, Jiangmen city, Guangdong Province (112.929°E,
22.728°N; altitude 60 m), about 80 km southwest from
Guangzhou urban area, 50 km southwest and 30 km
northeast from Foshan and Jiangmen urban area, respectively.
The site was heavily influenced by the intense air pollutant
emissions from Guangzhou and Foshan area in spring,
autumn and winter (Zhong et al., 2013; Peng et al., 2014).
Measurements were conducted in four different periods,
i.e., 5 to 24 August (summer), 30 September to 19 October
(autumn), and 29 November to 17 December (winter) in
the year of 2013, and 7 to 26 March (spring) in 2014, to
represent the four seasons, respectively. Correspondingly,
the average concentrations of the four periods were taken
as annual average values.
Instrumentation
Mass concentrations of PM2.5, its water-soluble ions
(SO42–, NO3– and NH4+) and the corresponding gaseous
precursors including HNO3, NH3, SO2 and NO2 were
measured on-line at the supersite.
The water-soluble inorganic ions in PM2.5 and gaseous
HNO3 and NH3 were detected by a Gas and Aerosol
Collector-Ion Chromatography (GAC-IC) system made in
Peking University, and the principle and configuration of
the GAC-IC system was similar to that introduced in detail
by Dong et al. (2012). In the system, a set of dull-polished
wet annular denuder with a steam jet aerosol collector was
employed for the continuous sampling of both gas- and
aerosol-phase pollutants. The inorganic gaseous and
particulate species were detected by two separate ion
chromatography (IC; ICS-90, Dionex, USA). The IC to
measure anions was equipped with a 4 × 25 mm guard
column (IonPac AG 14) followed by a 4 × 250 mm analytical
column (Ion Pac AS 14) with a mixture of 3.5 mM CO32–
and 1.0mM HCO3– as eluent solution. The other IC for
cations was installed with a 4 × 25 mm guard column (Ion
Pac CG 12) followed by a 4 × 250 mm analytical column
(IonPac CS 12) with 20 mM methane sulfonic acid as
eluent solution. Both ICs were electronically suppressed to
reduce the background signal. The inlet for the system was
set up with a URG PM2.5 cut-off with a flow rate of about
16.7 L min–1. The time resolution was 30 minutes, and the
measured data was hourly averaged for analysis. The
detection limits of gaseous HNO3 and NH3 were 0.183 µg m–3
and 0.023 µg m–3, respectively, and those for SO42–, NO3–
and NH4+ were 0.159 µg m–3, 0.034 µg m–3, and 0.030 µg m–3.
The amounts of the collected liquefied gaseous and particulate
pollutants of each sample were recorded to judge the
stability of this system, and standard samples were detected
before and after each separate measurement period in the
four different seasons to ensure the consistence of the data.
PM2.5 mass concentration was measured by a tapered
element oscillating microbalance (Model TEOM 1405),
SO2 by a trace level SO2 analyzer (Model 43iTLE), NO2 by
a trace level NO/NO2/NOx analyzer (Model 42iTL), and O3
by a UV spectrophotometry O3 analyzer (Model 49i); these
instruments were produced by the Thermo Fisher Scientific,
USA.
In addition, particle number size distributions and
meteorological parameters including temperature, RH,
precipitation, wind speed (WS), wind direction (WD),
UVA and visibility were also measured in this research.
Particle number size distributions from 3 to 900 nm were
monitored by a couple of scanning mobility particle sizers
(TSI model 3936, TSI Inc., St. Paul, MN, USA). UVA was
detected by a multiband ultraviolet radiation meter (Model
UV-S-A-T/UV-S-B-T, Kipp&Zonen B.V., Holland);
visibility was measured by a Belfort Model 6000 visibility
detection instrument from USA, and the other meteorological
parameters were reported by a portable weather station
(Model WXT520, Vaisala, Finland).
RESULTS AND DISCUSSION
Meteorological Conditions
Meteorological conditions of the four seasons in the PRD
region are distinct. Table 1 shows selected meteorological
parameters for four seasons at the supersite. Overall, mean
temperature and RH exhibited obvious seasonality with the
highest values in summer and the lowest values in winter.
Total precipitation was virtually insignificant in autumn
while abundant in summer. UVA and atmospheric visibility
also peaked in summer, but showed troughs during spring
instead of in winter, resulted from a special continuous wet
weather called Huinan Weather with very high RH occurred
in spring. As expected, the predominant wind direction was
northeast except south in summer. In general, higher wind
speeds were frequently observed in summer.
 Yue et al., Aerosol and Air Quality Research, 15: 1737–1747, 2015
Table 1. Selected meteorological parameters in the four seasons.
Temperature Relative humidity Precipitation
(°C) (%) (mm)
Average Average Total amount
Spring 17.2 71.7 5.9
Summer 28.0 76.7 183.5
Autumn 25.5 58.2 0.1
Winter 14.7 57.4 94.5
General Observations
The annual average mass concentration of PM2.5 was
64.2 µg m–3, higher than the secondary grade mass
concentration limit of the National Ambient Air Quality
Standards (GB 3095-2012) in China (35 µg m–3) by 83.4%.
The annual average concentrations of SO42–, NO3– and NH4+
were 16.6 µg m–3, 9.0 µg m–3 and 10.2 µg m–3, respectively,
with total contribution to PM2.5 (SNA/PM2.5) of 55.8%. It
was significantly higher than those measured at other
places of China, such as Shangdianzi regional site in North
China (Meng et al., 2013), Xi’an (Han et al., 2009), Beijing,
Chongqing, and Shanghai (Yang et al., 2011), indicating
the important role of secondary transformation played in
the PM2.5 pollution in the PRD region. Among the major
gaseous precursors of the water-soluble ions, the annual
concentration of SO2 was 31.6 µg m–3, meeting the National
Ambient Air Quality Standards (GB 3095-2012). However,
the annual average concentration of NO2 was 47.9 µg m–3 in
violation of the national standards, indicating the significant
influence from vehicle emissions. Due to high chemical
activity and its sticky nature, the atmospheric lifetime of
HNO3 was relatively short, leading to low concentration
level with annual average of 3.3 µg m–3, compared with other
species. However, the HNO3 concentrations were higher
than those at other places such as in North Carolina, USA of
0.9 µg m–3 (Walker et al., 2006), in Oberbärenburg, Germany
of 0.8 µg m–3 (Plessow et al., 2005) and at Hong Kong
urban area of 1.3 µg m–3 (Yao et al., 2006). In addition, the
daily peak concentrations of HNO3 were 1.8–18.6 µg m–3,
significantly higher than those in Mexico City of 1.4–8.4
µg m–3 (Zheng et al., 2008) and at Beijing urban area of < 8
µg m–3 (Yue et al., 2013). Both provided an evidence for
the strong oxidizing property of the atmosphere in the PRD
region. The annual average NH3 concentration was 15.2
µg m–3, obviously higher than that at Shangdianzi regional
site in North China of 8.7 µg m–3 (Meng et al., 2013). It
suggested that active agricultural production (e.g., composting
and N-fertilizer application), livestock feeding, and biological
activity imposed important effect on the atmosphere in the
PRD region and higher temperature was also probably one
of the key factors leading to higher NH3 concentration at
the supersite than that in North China, as industrial process,
vehicle emission and biomass combustion contributed a total
of less than 10% to NH3 sources in Guangdong Province
(Pan et al., 2014).
As diagrammed in Fig. 1, concentrations of PM2.5, SO42–
and NH4+ had the same seasonal variation pattern: winter >
autumn > spring > summer, and the rank of NO3–
1739
Wind speed UVA Visibility
Wind direction
(m s–1) (W m–2) (km)
Average
Predominant Average Average
(75 Percentile)
1.5 (2.0) NE 5.3 7.5
2.0 (2.7) S 11.0 19.3
1.6 (2.0) NE 9.8 10.8
1.8 (2.2) NE 5.7 8.9
concentrations was the same as that in Hong Kong (Louie
et al., 2005): winter > spring > autumn > summer; all
showed highest values in winter and lowest ones during
summer. The weather over PRD region during wintertime
is influenced by Siberian cold current as East Asian winter
monsoon is mainly influenced by Siberian High during this
time (Wu and Wang, 2002). The weak to moderate
northeasterly winds with increased air parcel residence
time over potential source regions in winter in the PRD
region (Louie et al., 2005) favored the accumulation,
condensation, and transformation of atmospheric pollutants
and the strong northerly winds can bring superregional
transport pollutants to the PRD region, both leading to high
concentrations of PM2.5 and its chemical components.
During summer, a low-pressure trough draws moist warm
air inland from the ocean with an increase in precipitation.
Frequent precipitation and good dispersion conditions for
air pollutants brought good air quality with low concentrations
of particles in summer. Two possible reseasons for the
higher NO3– concentration in spring than autumn which
was different from that of PM2.5, SO42– and NH4+ were as
follows: (1) Although the intense solar radiation in autumn
was favorable for NO3– formation through oxidation reaction,
the high temperature and low RH pushed the equilibrium of
NH3(g) + HNO3(g) < = > NH4NO3(s,aq) to produce gaseous
NH3 and HNO3, which was confirmed in the subsequent
discussions on gas to particle conversion. (2) The lower
gaseous precursor concentrations of NO2 and HNO3 than
those in spring would also lead to lower NO3– concentration.
HNO3 showed a consistent seasonal variation pattern
(winter > spring > autumn > summer) with NO2 and NO3–,
but the average concentrations of HNO3 in spring (3.7 µg m–3)
and autumn (3.3 µg m–3) were close with a difference of
around 10%. The dominant daytime source of HNO3 is
through the oxidation of NO2 by the hydroxyl radical.
HNO3 deposition is normally considered to be a terminal
sink of NOx, but recent studies have indicated that HNO3
deposited on the surface can be released back into the
atmosphere in the form of NO2 after heterogeneous reactions
with NO (Saliba et al. 2001). In addition, HNO3·H2O
complex could be photolyzed into HONO or NO (Ramazan
et al., 2006). Solar radiation was a double-edged sword for
HNO3. In summertime, clean south wind from South China
Sea usually dilutes the pollutants over PRD region and
improves the air quality and visibility to large extent. The
precursors of HNO3, NO2 and OH radical should also be
low to produce HNO3 during the time when southerly wind
is prevalent, even though there is existence of strong solar
1740 Yue et al., Aerosol and Air Quality Research, 15: 1737–1747, 2015
Concentrations (μg m‐3) 120
100
80
60
40
20
0
PM2.5 SO42‐ NO3‐
Fig. 1. Concentrations of O3, PM2.5 and the water-soluble ions and their major gaseous precursors during different seasons.
radiation. Similarly, NO2 was recorded to be lower during
the autumn than in spring and winter, unlikely to cause
high HNO3 in the autumn either.
The seasonal variation of NH3 concentrations was unique
in this research with the highest average concentration in
spring and the lowest one in winter. It was also different
from NH3 variation mode at the Shangdianzi regional site
in North China with highest concentrations occurred in
summer, as over there agricultural activity was a major
source of NH3 and the main compositions of the fertilizer
used were diammonium phosphate and urea, which are
very easy to volatile and produce NH3 in summer, and the
high temperature makes against the reaction of NH3 and
HNO3 to form particulate NH4NO3 (Meng et al., 2013).
NH3 observation of this work was also different from the
one observed by Zheng et al. (2015) in an industry zone of
Nanjing, which was heavily influenced by industry emissions.
However, the atmospheric temperature in the PRD region
is significantly higher than that in North China, and
meteorological conditions favoring agricultural production
appeared earlier in a year, so the agricultural activity such
as composting and fertilization will be more active during
spring than summer, resulting in more NH3 emission.
Moreover, the far higher relative humidity in summer is in
favor of the formation and existence of NH4NO3. Affected
by such complex factors, the highest seasonal average NH3
concentrations in PRD appeared in spring followed by that in
summer. NH3 concentrations at the supersite were obviously
higher than those in Beijing and at Xinken during the same
seasons (Yue et al., 2013; Hu et al., 2008).
Diurnal Variations of the Pollutants
The diurnal variations of the average temperature, RH,
wind speed, UVA, PM2.5, water-soluble ions, O3, HNO3,
SO2 and NH3 during the measuring period are shown in
Fig. 2. The lowest temperature occurred in the morning at
about 6 o’clock (18.8°C), and the maxima in the afternoon
at about 15 o’clock of 24.3°C. The diurnal variation pattern
of RH was the inverse of temperature with maxima in the
early morning and minima around 14 o’clock. The highest
average wind speed was observed at noon of about 2 m s–1.
In contrast, the wind speeds in the early morning were lower.
This trend of wind speed diurnal variation was different from
that observed at a coastal regional site in the PRD region
Spring
Summer
Autumn
Winter
NH4+ SO2 NO2 HNO3 NH3 O3
Pollutants
with higher wind speed in the morning (Hu et al., 2008).
The UVA increased quickly after sun rise and showed peak
values at noon with obvious decrease in the afternoon
followed, and come to nearly zero at night. Overall, the
meteorological conditions in the afternoon were characterized
by high wind speed, high temperature, and low RH. In
addition, the boundary layer height was expected to be
higher in the afternoon. Early in the morning, by contrast,
it was characterized with low wind speed, low temperature,
high RH, and low boundary layer height. That is to say, it
was favorable for the dispersion and dilution of the pollutants
in the afternoon while beneficial for pollutant accumulation
and gas to particle transformation early in the morning. It
was the main causes for the fact that PM2.5 and its inorganic
aerosol ions showed lower concentrations in the afternoon
and higher ones early in the morning. SO2 and NH3, mainly
from primary emission sources, also showed similar diurnal
variation trends. In contrast, the diurnal variations of O3
and HNO3 were similar to that of UVA, but with later peak
time, as they are products of atmospheric photochemistry
reactions.
Contributions of Secondary Ions to PM2.5
The contributions of SO42–, NO3– and NH4+ to PM2.5 are
shown in Fig. 3. Overall, they contributed 25.9%, 14.0%,
and 15.9% to PM2.5, respectively. Among them, SO42– was
the biggest contributor, with a small fluctuation range of
23.9–27.4% in different seasons. The contributions of
NH4+ were 12.7–17.7%, but the fractions of NO3– varied
significantly, from 6.3% in summer to 19.2% in winter.
The total contribution of SNA/PM2.5 changed from 45.6%
to 64.3%, showing high values during spring and winter
but low ones in summer and autumn. The reasons for the
low fraction during summer and autumn are as follows: (1)
Biological activity during these seasons is vigorous and
will emit a large amount of volatile and semi-volatile
organic compounds, supplying abundant precursors for
organic aerosols. (2) The intense solar radiation provides a
good condition for the photochemical reactions to produce
secondary organic aerosols. As reported that the secondary
organic matters accounted for 56% in the organic fine
aerosols in Shenzhen in PRD during summer, while in
winter the fraction was only 6% (Niu et al., 2006). In short,
the increase in organic matter contribution was probably
 Yue et al., Aerosol and Air Quality Research, 15: 1737–1747, 2015 1741

25 80 2.5 30

Relative hunidity (%)

23 2.0
70

Wind speed ms-1)

Temperature (℃)

UVA (W m-2)
20
21 1.5
60
19 1.0
10
50
17 T RH 0.5 WS UVA

15 40 0.0 0
0 3 6 9 12 15 18 21 24 0 3 6 9 12 15 18 21 24
80 Local time (h) 90 Local time (h)
25 50
70 80
60 70 20 40
PM2.5 (μg m-3)

m-3)
60

SO2 (μg m-3)

O3 (μg m-3)
50 15 30
50

SO4 (μg
40
40
10 20

2-
30 30
20 20
PM2.5 O3 5 SO4 SO2 10
10 10
0 0 0 0
0 3 6 9 12 15 18 21 24 0 3 6 9 12 15 18 21 24
14 Local time (h) 25 12 Local time (h) 5
12 10
20 4
10

HNO3 (μg m-3)

NH4+ (μg m-3)

m-3)
NH3 (μg m-3)

8
8 15 3
NO3 (μg

6
6 10 2
-

4
4
NH4 NH3 5 2 NO3 HNO3 1
2
0 0 0 0
0 3 6 9 12 15 18 21 24 0 3 6 9 12 15 18 21 24
Local time (h) Local time (h)
Fig. 2. Average diurnal variations of selected parameters during the whole measurement.

the proximate cause for the obvious decrease in water-soluble Tao et al., 2010; Yue et al., 2013). The abundant NH3 at
inorganic ion contribution to PM2.5. The seasonal fraction the supersite was the major cause for the high equivalence
of SNA/PM2.5 at the supersite was significantly higher than charge ratio of [NH4+]/(2[SO42–] + [NO3–]).
those in Guangzhou of 36.7% in summer and of 41.3% in
winter (Tao et al., 2010; Huang et al., 2014). Gas to Particle Conversion
The linear correlation between SO42– and NH4+ (R2 = 0.55
Charge Balance of SO42–, NO3– and NH4+ or 0.68) was significantly better than that between NO3–
The mean molar ratio of NH4+ to SO42– was 3.3, far more and NH4+ (R2 = 0.27 or 0.36) during summer and autumn,
than 2, indicating that abundant NH3 was present to respectively; while such linear correlation was comparable
neutralize H2SO4 and NH4HSO4 was negligible. The excess during winter and spring, with R2 of 0.79 and 0.85 for the
of NH4+ was inferred to be associated with NO3– and Cl–. former and R2 of 0.75 and 0.84 for the latter. It indicated
The annual average equivalence charge ratio of [NH4+]/ that the heterogeneous reaction between HNO3 and NH3 in
(2[SO42–] + [NO3–]) at the supersite was 1.2, implying that the particle-phase to form NH4NO3 probably played a more
NH4+ in PM2.5 can totally balance SO42– and NO3–, and important role in winter and spring than in summer and
mainly existing in the form of (NH4)2SO4 and NH4NO3. autumn. In order to determine if the meteorological
The average equivalence charge ratios in different seasons conditions, mainly atmosphere temperature and RH, at the
were comparable, being 1.1 in summer and winter, and 1.2 supersite favor the formation of NH4NO3 or not, the
in spring and autumn. They were larger than those in measured concentration product (Km = [NH3] × [HNO3]) of
Guangzhou, Xinken, Beijing, Shanghai and Xi’an in the HNO3 and NH3 was calculated using the measured data
range of 0.5–0.9, where NH4+ cannot balance the entire and then compared with the theoretical equilibrium constant
SO42– and NO3–, and a part of NO3– may be in the form of (Ke) calculated according to the method mentioned in
KNO3 (Wang et al., 2006; Zhang et al., 2007; Hu et al., 2008; (Mozurkewich, 1993). The data were divided into two
1742 Yue et al., Aerosol and Air Quality Research, 15: 1737–1747, 2015

Annual average

Spring Summer

Autumn Winter
Fig. 3. Contributions of different chemical compositions to PM2.5.

groups: (1) The ambient RH was below the deliquescence
relative humidity (DRH); (2) The ambient RH was above
the DRH. For the latter, the existence of SO42– in the
deliquescent aerosol particles reduces Ke compared to that
of pure NH4NO3 solution (Stelson and Seinfeld, 1982). The
ionic strength fraction (γ) of NH4NO3 in NH4+/NO3–/SO42–
system can be calculated according to (Stelson and Seinfeld,
1982): γ = [NH4NO3]/([NH4NO3] + 3[(NH4)2SO4]). And
Ke* for this system was derived by multiplying Ke with γ
and was compared with Km. Ke (Group 1) or Ke* (Group 2)
larger than Km suggests that NH4NO3 tends to dissociate
and conversely the formation of NH4NO3 is possible.
The ratios of Km/Ke (or Km/Ke*, Ke* was used when RH
is larger than the DRH through the paper) by hour at the
supersite in four seasons were derived, and categorized into
two types according to whether it was below 1. As shown
in Table 2, Km was mostly larger than Ke (or Ke*) during
spring and winter; while in over 60% of the time in
summer and autumn, Km was less than Ke (or Ke*). One
possible cause was that HNO3 concentrations were much
higher during spring and winter than in summer and autumn.
The lower temperature in spring and winter (< 20°C on
average) than those in summer and autumn (> 25°C on
average) was probably also an important factor. It has been
also reported that Ke was larger during daytime and smaller
at night than Km in autumn at Xinken site (Hu et al., 2008),
presenting less NH3 and NH4+ but more HNO3 and NO3–
than those at supersite.
 Yue et al., Aerosol and Air Quality Research, 15: 1737–1747, 2015
Table 2. Percentages of the Km/Ke (or Km/Ke*) ratios during different seasons.
Spring
Km/Ke (or Km/Ke*) < 1 6.5%
Km/Ke (or Km/Ke*) ≥ 1 93.5%
Case Study
Autumn and winter are the period with heavy air
pollution and frequent regional haze in the PRD region;
while the comparison between Km and Ke implies that the
characteristics of particle pollution in the two different
seasons will be distinct. Consequently, a complex air
pollution episode with both daily PM2.5 and O3 concentrations
violating the secondary grade concentration limit of the
National Ambient Air Quality Standards (75 µg m–3 and
200 µg m–3, respectively) in autumn and a particle pollution
episode with daily PM2.5 exceeding the secondary grade
concentration limit of the same standards but low O3
concentrations in winter were discussed respectively to
investigate the different mechanisms of such episodic cases.
A Complex Pollution Episode in Autumn
Due to the strong solar radiation in autumn, PM2.5 and
O3 frequently exceeded the national standards even on the
same day. The pollution episode from 2 to 6 October 2013
was a typical example (Fig. 4). The daily maximum UVA
was 38–50 W m–2; wind speed showed a clear diurnal
variation which increased during daytime to around 3 m s–1;
temperature and RH varied in the ranges of 22–31°C and
30–74%, respectively. On the whole, the conditions were
not favorable for pollutant accumulation but beneficial for
secondary transformation related with atmospheric
photochemical reactions. HNO3 had a similar diurnal
variation trend to O3, since both of them were produced
from atmospheric photochemical reactions, and O3 provided
hydroxyl radical for NO2 oxidation and thus increased the
HNO3 concentration concurrently. The trends among NO3–,
NH4+ and NH3 were just in opposite. This observation can
be explained by the development of the planetary boundary
layer as the day progressed. Also, it has been suggested
that gas-particle partitioning can play a dominant role in
the fate of aerosol ammonium nitrate over a large spatial
scale (DeCarlo et al., 2008). During the polluted days from
3 to 5 October, Km/Ke was below 1 during daytime, indicating
that NH4NO3 tended to dissociate. As clearly illustrated in
Fig. 4 that aerosol NO3– concentration and the mass ratio of
[NO3–]/[SO42–] showed increasing trends, and the theoretical
equilibrium constant was lower than the product of observed
concentrations at night, implying that the formation of
NH4NO3 was favored. SNA contributed around 60% to PM2.5
and sulfate played a more important role in the fine particle
pollution. On the days of 2 and 6 October, new particle
formation events with burst and obvious growth of ultrafine
particles especially significant increase of the nucleation
mode particle number concentration (Wu et al., 2007, Yue
et al., 2009) were observed with lower concentrations of
PM2.5. During these days, most of the ratios of Km/Ke were
below 1 even at night and the mass ratios of [NO3–]/[SO42–]
kept at low levels. Therefore, it was unlikely that NO3–
1743
Summer Autumn Winter
73.9% 66.3% 4.8%
26.1% 33.7% 95.2%
participated in new particle formation. Different fractions
of SNA/PM2.5 was probably due to the fact that the new
particle formation event on 2 October was mainly dominated
by H2SO4 and NH3, while organic compounds might
contribute significantly to the event on 6 October (Yue et
al., 2010b). In addition, the burst and subsequent growth of
ultrafine particles on every single day during this episode
especially with high PM2.5 mass concentrations should be
an indicator for the strong atmospheric oxidizing property
in autumn of the PRD region.
A Particle Pollution Episode in Winter
A particle pollution episode with daily PM2.5 concentrations
violated the second grade limit of the national standards
but low O3 concentrations was observed during 30 November
to 5 December in 2013. Time series of selected parameters
during this period were illustrated in Fig. 5. During this
episode, the daily maximum UVA was 26–38 W m–2,
significantly lower than that during the complex air pollution
episode in autumn, causing obviously lower O3
concentrations. The wind speed was relative low (< 2 m s–1),
indicating stagnant atmospheric conditions, which were
favorable for the accumulation and transformation of air
pollutants. The RH variation range was 21–78%, similar to
that during the complex air pollution episode in autumn,
while the temperature was significantly lower, in the range
of 10–23°C, leading to very low Ke and high ratios of
Km/Ke, and promoting the gas to particle conversion of
HNO3 and NH3 to form NH4NO3. HNO3 also showed high
concentrations during the daytime and low ones at night,
similar to the trend of O3. SNA accounted for about 60% of
PM2.5. The SO42– concentration was generally higher than
that of NO3–. However, from the late afternoon on 2
December to early morning on 4 December with low
temperature and high RH, concentrations of NO3– exceeded
SO42– most of the time, concurring with high concentrations
of PM2.5. The ratios of Km/Ke were also higher than 1, with
particularly higher values on 3 and 4 December. The quick
and effective gas to particle conversion of HNO3 and NH3
to NH4NO3 should be the major cause for the higher NO3–
concentrations than SO42–. No new particle formation events
were observed during this episode, probably because of the
low UVA values and high concentration of PM2.5, indicating
weak source but strong sink for the newly formed particles
and their precursors.
CONCLUSIONS
The concentrations of PM2.5, its water-soluble inorganic
ions and the related gaseous precursors during four seasons
were measured and discussed at the regional atmospheric
supersite in the PRD region. The average concentrations of
PM2.5, SO42–, NO3– and NH4+ were 64.2 µg m–3, 16.6 µg m–3,
1744 Yue et al., Aerosol and Air Quality Research, 15: 1737–1747, 2015

4 WS WD 360

Wind direction(°)
Wind speed(ms‐1)
3 270

2 180

1 90

0 0
35 10‐2 10‐3 10‐4 10‐5 10‐6 10‐780
T RH
70
Temperature(℃)

30
60

RH(%)
25 50
40
20
30
15 20
150 10‐2 10‐3 10‐4 10‐5 10‐6 10‐7350
  PM2.5 300
120
O3 250
PM2.5(μgm‐3)

O3(μgm‐3)
90 200
60 150
100
30
50
0 0
50 10‐2 10‐3 10‐4 10‐5 10‐6 10‐7
  NO3 SO4 NH4
Concentration (μgm‐3)

40

30

20

10

0
4 10‐2 10‐3 10‐4 10‐5 10‐6 10‐740
  HNO3 NH3
3 30
HNO3(ppb)

NH3(ppb)
2 20

1 10

0 0
0.8 10‐2 10‐3 10‐4 10‐5 10‐6 10‐7
  NO3/SO4 SNA/PM2.5
0.6
Ratio

0.4

0.2

0.0
2.5 10‐2 10‐3 10‐4 10‐5 10‐6 10‐7
 
2.0 Km/Ke
Ratio of Km/Ke

1.5

1.0

0.5

0.0
10‐2 10‐3 10‐4 10‐5 10‐6 10‐7
Time (m‐d)

10‐2 10‐3 10‐4 10‐5 10‐6 10‐7

Time (m‐d)

Fig. 4. Time series of selected parameters from 2 to 6 October.

 Yue et al., Aerosol and Air Quality Research, 15: 1737–1747, 2015 1745

4 360
WS WD

Wind speed(ms‐1)
3 270

WD(°)
2 180

1 90

0 0
2511‐30 12‐1 12‐2 12‐3 12‐4 12‐5 12‐690
T RH
Temperature(℃)

20
60

RH(%)
15
30
10

5 0
200 11‐30 12‐1 12‐2 12‐3 12‐4 12‐5 12‐6
  PM2.5 O3
Concentration (μgm‐3)

160

120

80

40

0
10011‐30 12‐1 12‐2 12‐3 12‐4 12‐5 12‐6
  NO3 SO4 NH4
Concentration (μgm‐3)

80

60

40

20

0
411‐30 12‐1 12‐2 12‐3 12‐4 12‐5 12‐650
HNO3 NH3
40
3
HNO3(ppb)

NH3(ppb)

30
2
20
1
10

0 0
50.0 11‐30 12‐1 12‐2 12‐3 12‐4 12‐5 12‐6
 
40.0 Km/Ke
Ratio of Km/Ke

30.0

20.0

10.0

0.0
11‐30 12‐1 12‐2 12‐3 12‐4 12‐5 12‐6
Time (m‐d)
Fig. 5. Time series of selected parameters from 30 November to 5 December.

9.0 µg m–3, and 10.2 µg m–3, respectively. SNA accounted particle pollution in the PRD region. NH3 concentrations
for 55.8% of PM2.5 on average, reflecting the significant were highest in spring and lowest in winter with an annual
influence of the secondary transformation in the fine average value of 15.2 µg m–3. Such abundant NH3 facilitated
1746 Yue et al., Aerosol and Air Quality Research, 15: 1737–1747, 2015
the neutralization of H2SO4 and HNO3 with the average
equivalent charge ratio of [NH4+]/(2[SO42–] + [NO3–])
being 1.1, suggesting that NH4+, SO42– and NO3– should be
mainly in the form of (NH4)2SO4 and NH4NO3 in PM2.5.
The high HNO3 concentrations provided an evidence for
the strong oxidizing capability of the atmosphere in the
PRD region.
The seasonal average SNA/PM2.5 contributions varied
from 46.0% to 64.3%, lower in summer and autumn, and
higher in winter and spring. The contributions of SO42– and
NH4+ to PM2.5 were relatively stable, which fluctuated in
the range of 23.9–27.4% and 12.7–17.7%, respectively;
while the contributions of NO3– in different seasons were
diverse with a large fluctuation range of 6.3–19.2%. During
winter and spring, the comparable linear correlations of
NO3– versus NH4+ (R2 = 0.75 or 0.84) and SO42– versus
NH4+ (R2 = 0.79 or 0.85), the higher ratios of Km/Ke, and
larger contributions of NO3– to PM2.5 reflected that the
heterogeneous reaction between HNO3 and NH3 to form
NH4NO3 in the particle-phase played a more important role in
fine particle pollution. And the fast and effective gas to
particle convention of HNO3 and NH3 to NH4NO3 can
cause even higher concentrations of NO3– than SO42– during
some pollution cases in winter.
Overall, the strong atmospheric oxidizing property and
NH3 played significant roles in the fine particle pollution in
the PRD region, and effective NH3 control measures will
lead to substantial reduction in PM2.5 mass concentration
and the frequency of haze events.
ACKNOWLEDGEMENT
This work was supported by the National Natural
Science Foundation of China (41303075 and U1301234),
the Guangdong Provincial Natural Science Foundation
(S2012020011044) and the major national scientific
instrument and equipment development project
(2013YQ060569).
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Received for review, December 25, 2014
Revised, March 9, 2015
Accepted, April 25, 2015